WO2002061025A1 - Hydroxy-ethers mixtes a haut degre d'ethoxylation utilises comme agents antimoussants - Google Patents

Hydroxy-ethers mixtes a haut degre d'ethoxylation utilises comme agents antimoussants Download PDF

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Publication number
WO2002061025A1
WO2002061025A1 PCT/EP2002/001052 EP0201052W WO02061025A1 WO 2002061025 A1 WO2002061025 A1 WO 2002061025A1 EP 0201052 W EP0201052 W EP 0201052W WO 02061025 A1 WO02061025 A1 WO 02061025A1
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Prior art keywords
formula
alkyl
hydroxy mixed
mixed ethers
contain
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PCT/EP2002/001052
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German (de)
English (en)
Inventor
Karl Heinz Schmid
Detlev Stanislowski
Hans-Christian Raths
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Cognis Deutschland Gmbh & Co. Kg
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Priority claimed from DE2001114172 external-priority patent/DE10114172A1/de
Priority claimed from DE2001116020 external-priority patent/DE10116020A1/de
Application filed by Cognis Deutschland Gmbh & Co. Kg filed Critical Cognis Deutschland Gmbh & Co. Kg
Priority to EP02719749A priority Critical patent/EP1356014B1/fr
Priority to US10/470,898 priority patent/US6921744B2/en
Priority to ES02719749T priority patent/ES2373872T3/es
Publication of WO2002061025A1 publication Critical patent/WO2002061025A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0026—Low foaming or foam regulating compositions
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
    • C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
    • C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C11D1/721—End blocked ethers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/825—Mixtures of compounds all of which are non-ionic
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2068—Ethers

Definitions

  • the invention relates to highly ethoxylated hydroxy mixed ethers in conjunction with detergents, dishwashing detergents and cleaning agents, and to the use of such hydroxy mixed ethers as defoamers in detergents, dishwashing detergents and cleaning agents.
  • Means for rinsing and cleaning hard, non-textile surfaces that occur in the household and commercial sector should mostly develop a small volume of foam when used, which will decrease significantly within a few minutes.
  • Means of this kind have been known for a long time and are established on the market. These are essentially aqueous surfactant solutions of various types with or without the addition of builders, solubilizers (hydrotropes) or solvents. To prove the effectiveness at the beginning of the cleaning work, the consumer wants a certain amount of foam in the application solution, but the foam should collapse quickly so that once cleaned surfaces do not have to be wiped off.
  • agents of the type mentioned are usually mixed with low-foaming nonionic surfactants.
  • Rinse aids are therefore used to obtain clear, spotless dishes.
  • the addition of liquid or solid rinse aid, which can be added separately, or already in ready-to-use form with the cleaning agent and / or regeneration salt together (“2 in 1", “3 in 1", eg in the form of tabs and powders), ensures that the water runs off the dishes as completely as possible, so that the different surfaces are residue-free and shiny at the end of the wash program.
  • Commercial rinse aids are mixtures of, for example, nonionic surfactants, solubilizers, organic acids and solvents, water and possibly preservatives and fragrances.
  • the task of the surfactants in these agents is to influence the interfacial tension of the water so that it is as thin and coherent as possible Film can run off the wash ware, so that no water drops, streaks or films remain during the subsequent drying process (so-called wetting effect or wetting behavior).
  • surfactants in rinse aids also have to dampen the foam that arises from food residues in the dishwasher. Since the rinse aid usually contains acids to improve the clear dry effect, the surfactants used must also be relatively insensitive to hydrolysis against acids.
  • Rinse aids are used both in the home and in commercial areas.
  • the rinse aid is usually added after the pre-rinse and cleaning cycle at just under 40 ° C - 65 ° C.
  • Commercial dishwashers work with only one cleaning liquor, which is only renewed by adding the rinse aid solution from the previous washing process. There is therefore no complete water exchange during the entire washing program. Therefore, the rinse aid must also have a foam-suppressing effect, be temperature-stable with a strong temperature gradient of a maximum of 85-35 ° C and also be sufficiently stable against alkali and active chlorine.
  • German published patent application DE 19738866 describes surfactant mixtures composed of hydroxymixed ether and nonionic surfactants, such as fatty alcohol polyethylene glycol / polypropylene glycol ether, optionally end-capped, which have very good foaming behavior and show excellent rinse aid effects in rinse aids.
  • the object of the present invention was to provide washing, rinsing and cleaning agents which at the same time have good foam and cleaning behavior, in particular very good
  • Drainage behavior i.e. an improvement in the wetting behavior on plastic surfaces as well as a high
  • the invention relates to hydroxy mixed ethers (HME) of the formula (I)
  • R 1 is a linear or branched alkyl and / or alkenyl radical having 4 to 22 carbon atoms
  • R 2 is a linear or branched alkyl and / or alkenyl radical having 2 to 22 carbon atoms x is 40 to 80.
  • Hydroxy mixed ethers are known from the literature and are described, for example, in German application DE 19738866.
  • R 2 CHOCH2 1,2-epoxyalkanes
  • R 2 is an alkyl and / or alkenyl radical having 2 to 22, in particular 6 to 16, carbon atoms, with alkoxylated alcohols.
  • Preferred hydroxy mixed ethers for the purposes of the invention are those derived from alkoxylates of monohydric alcohols of the formula R 1 -OH having 4 to 18 carbon atoms, where R 1 is an aliphatic, saturated, straight-chain or branched alkyl radical, in particular having 6 to 16 carbon atoms, stands.
  • Suitable straight-chain alcohols are butanol-1, capron, ⁇ nanth, capryl, pelargon, caprinal alcohol, undecanol-1, lauryl alcohol, tridecanol-1, myristyl alcohol, pentadecanol-1, palmityl alcohol, heptadecanol-1, stearyl alcohol, Nonadecanol-1, arachidyl alcohol, heneicosanol-1, behenyl alcohol and their technical mixtures, as they occur in the high-pressure hydrogenation of technical methyl esters based on fats and oils.
  • branched alcohols examples include so-called oxo alcohols, which usually carry 2 to 4 methyl groups as branches and are produced by the oxo process, and so-called Guerbet alcohols, which are branched in the 2-position with an alkyl group.
  • Suitable Guerbet alcohols are 2-ethylhexanol, 2-butyloctanol, 2-hexyldecanol and / or 2-octyldodecanol.
  • the alcohols are used in the form of their alkoxylates, which are reacted by reacting the alcohols with
  • Ethylene oxide can be produced in a known manner.
  • Alkoxylates of alcohols which are formed by reaction with 40 to 80 mol of ethylene oxide are preferably used.
  • Hydroxy mixed ethers having 40 to 60 ethylene oxide units are particularly preferred.
  • Preferred hydroxy mixed ethers for the purposes of the invention are those derived from ethoxylates of monohydric alcohols of the formula R 1 -OH having 6 to 18 carbon atoms, preferably 6 to 16 and in particular 8 to 10 carbon atoms, where R 1 is a linear alkyl radical and x for 40 to 60.
  • Hydroxy mixed ethers of the formula (I) are very particularly preferred, where R1 is an alkyl radical having 8 to 10 carbon atoms, in particular based on a native fatty alcohol, R2 is an alkyl radical having 10 carbon atoms, in particular a linear alkyl radical and x is 40 to 60.
  • agents which contain hydroxy mixed ethers according to the invention, as well as further ingredients customary in washing, rinsing and cleaning agents.
  • these customary ingredients can be alkyl and / or alkenyl oligoglycosides, other nonionic surfactants, anionic surfactants, builders, enzymes and other auxiliaries and additives.
  • the agents according to the invention contain alkyl and / or alkenyl oligoglycosides of the formula (II).
  • R 5 is an alkyl and / or alkenyl radical having 4 to 22 carbon atoms
  • G is a sugar radical having 5 or 6 carbon atoms
  • p is a number from 1 to 10.
  • the alkyl and / or alkenyl oligoglycosides can be derived from aldoses or ketoses with 5 or 6 carbon atoms, preferably glucose.
  • the preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligoglucosides.
  • the alkyl radical R 5 can be derived from primary saturated alcohols. Typical examples are butanol-1, capron, ⁇ nanth, capryl, pelargon, caprinal alcohol, undecanol-1, lauryl alcohol, tridecanol-1, myristyl alcohol, pentadecanol-1, cetyl alcohol, palmity alcohol, heptadecanol-1, stearyl alcohol, isostearyl alcohol , Nonadecanol-1, arachidyl alcohol, heneicosanol-1, and behenyl alcohol and their technical mixtures, such as are obtained for example in the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from Roelen's oxosynthesis.
  • the alkenyl radical R 5 can be derived from primary unsaturated alcohols.
  • unsaturated alcohols are undecen-1-ol, oleyl alcohol, elaidyl alcohol, ricinol alcohol, linoleyl alcohol, linolenyl alcohol, gadoleyl alcohol, arachidone alcohol, eruca alcohol, brassidyl alcohol, palmoleyl alcohol, petroselinyl alcohol, arachyl alcohol, and their technical mixtures, which can be obtained as described above, and their technical mixtures.
  • Alkyl or alkenyl radicals R 5 which are derived from primary alcohols having 6 to 16 carbon atoms are preferred.
  • alkyl oligoglucosides of the chain length Cs-Cio which are obtained as a preliminary step in the separation of technical C ⁇ -Ci ⁇ -coconut fatty alcohol by distillation and can be contaminated with a proportion of less than 6% by weight of Ci2-alcohol, as well as alkyl oligoglucosides based on technical C9 / 11-oxo alcohols.
  • the alkyl or alkenyl radical R 5 can also be derived from primary alcohols having 12 to 14 carbon atoms.
  • Alkyl and / or alkenyl oligoglycosides of the formula (II) are preferably used, p being numbers from 1 to 3 and R 5 being an alkyl radical having 6 to 16 carbon atoms.
  • the agents according to the invention contain 0.01 to 25% by weight, preferably 0.025 to 20% by weight and in particular 0.1 to 15% by weight of hydroxy mixed ethers of the formula (I), calculated as active substance, based on the agents.
  • Active substance is defined as the mass of surfactants (calculated as 100% pure substance) contained in the agent.
  • the agents according to the invention contain 0.01 to 30% by weight, preferably 0.1 to 20% by weight and in particular 0.2 to 15% by weight of alkyl and / or alkenyl oligoglycosides of the formula (II), calculated as the active substance , based on the funds.
  • the agents according to the invention can contain further nonionic surfactants.
  • Typical examples of nonionic surfactants are alkoxylates of alkanols, end-capped alkoxylates of alkanols without free OH groups, alkoxylated fatty acid lower alkyl esters, amine oxides, alkylphenol polyglycol ethers, fatty acid polyglycol esters, fatty acid amide polyglycol ethers, fatty amine polyglycol ethers, alkoxylated triglycerol ethers, fatty glucose amides, mixed glycidyl amides, mixed acid amides, mixed acid amides, and mixed acid amides (especially vegetable products based on wheat), polyol fatty acid esters, sugar esters, sorbitan esters, and polysorbates.
  • nonionic surfactants contain polyglycol ether chains, they can have a conventional, but preferably a narrow, homolog distribution.
  • the further nonionic surfactants are preferably selected from the group formed by alkoxylates of alkanols, in particular fatty alcohol polyethylene glycol / polypropylene glycol ether (FAEO / PO) of the formula (III) or fatty alcohol polypropylene glycol / polyethylene glycol ether (FAPO / EO) of the formula (IV), end-capped Alkoxylates of alkanols, especially end group closed fatty alcohol polyethylene glycol / polypropylene glycol ether or end-capped fatty alcohol polypropylene glycol / polyethylene glycol ether, and fatty acid lower alkyl esters and amine oxides.
  • alkoxylates of alkanols in particular fatty alcohol polyethylene glycol / polypropylene glycol ether (FAEO / PO) of the formula (III) or fatty alcohol polypropy
  • fatty alcohol polyethylene glycol / polypropylene glycol ethers of the formula (III), which are optionally end-capped, are optionally end-capped,
  • R 6 is an alkyl and / or alkenyl radical having 8 to 22 C atoms
  • R 7 is H or an alkyl radical having 1 to 8 C atoms
  • n is a number from 1 to 40, preferably 1 to 30 , in particular 1 to 15, and m represents 0 or a number from 1 to 10.
  • R 8 is an alkyl and / or alkenyl radical with 8 to 22 C atoms
  • R 9 for H or an alkyl radical with 1 to 8 C atoms
  • q for a number from 1 to 5 and r for a number of 0 up to 15
  • the agents according to the invention contain fatty alcohol polyethylene glycol / polypropylene glycol ether of the formula (III) in which R 6 is an aliphatic, saturated, straight-chain or branched alkyl radical having 8 to 16 carbon atoms, n is a number from 1 to 10, and m represents 0 and R 7 represents hydrogen.
  • R 6 is an aliphatic, saturated, straight-chain or branched alkyl radical having 8 to 16 carbon atoms
  • n is a number from 1 to 10
  • m represents 0
  • R 7 represents hydrogen.
  • Suitable representatives of non-end-capped representatives are those of the formula (III) in which R 6 is an aliphatic, saturated, straight-chain or branched alkyl radical having 8 to 16 carbon atoms, n is a number from 2 to 7, m is a number of 3 to 7 and R 7 represents hydrogen.
  • R 6 is an aliphatic, saturated, straight-chain or branched alkyl radical having 8 to 16 carbon atoms
  • n is a number from 2 to 7
  • m is a number of 3 to 7
  • R 7 represents hydrogen.
  • the end group-capped compounds of the formula (III) are capped with an alkyl group having 1 to 8 carbon atoms (R 7 ).
  • R 7 alkyl group having 1 to 8 carbon atoms
  • Such compounds are often referred to in the literature as mixed ethers.
  • Suitable representatives are methyl-capped compounds of the formula (III) in which R 6 is an aliphatic, saturated, straight-chain or branched alkyl radical having 8 to 16 carbon atoms, n is a number from 2 to 7, m is a number from 3 to 7 and R 7 represents a methyl group.
  • Such compounds can easily be prepared by reacting the corresponding non-end-capped fatty alcohol polyethylene glycol / polypropylene glycol ether with methyl chloride in the presence of a base.
  • Suitable representatives of alkyl-capped compounds are those of the formula (III) in which R 6 is an aliphatic, saturated, straight-chain or branched alkyl radical having 8 to 16 carbon atoms, n is a number from 5 to 15, m is 0 and R 7 represents an alkyl group with 4 to 8 carbon atoms.
  • the end group closure is preferably carried out with a straight-chain or branched butyl group by the corresponding fatty alcohol polyethylene glycol ether containing n-butyl chloride or partly. Butyl chloride is reacted in the presence of bases.
  • end-capped fatty alcohol polypropylene glycol / polyethylene glycol ethers of the formula (IV) may be present.
  • Such connections are described, for example, in German published patent application DE-A1- 43 23 252.
  • Particularly preferred representatives of the compounds of the formula (IV) are those in which R 8 is an aliphatic, saturated, straight-chain or branched alkyl radical having 8 to 16 carbon atoms, q is a number from 1 to 5, r is a number of 1 to 6 and R 9 represents hydrogen.
  • Suitable alkoxylated fatty acid lower alkyl esters are surfactants of the formula (V)
  • R 10 CO is a linear or branched, saturated and / or unsaturated acyl radical with 6 to 22 carbon atoms
  • R 11 for hydrogen or methyl
  • R 2 for linear or branched alkyl radicals with 1 to 4 carbon atoms
  • w for numbers from 1 to 20 stands.
  • Typical examples are the formal insert products of an average of 1 to 20 and preferably 5 to 10 moles of ethylene and / or propylene oxide in the methyl, ethyl, propyl, isopropyl, butyl and tert-butyl esters of caproic acid, caprylic acid, 2 -Ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachidic acid, gadoleic acid, behenic acid, and technical grade mixtures and erucas.
  • the products are usually prepared by inserting the alkylene oxides into the carbonyl ester bond in the presence of special catalysts, such as, for example, calcined hydrotalcite. Conversion products of an average of 5 to 10 moles of ethylene oxide into the ester linkage of technical coconut fatty acid methyl esters are particularly preferred.
  • the preparation of the amine oxides of the formula (VI) starts from tertiary fatty amines which have at least one long alkyl radical and is oxidized in the presence of hydrogen peroxide.
  • R 13 represents a linear or branched alkyl radical with 6 to 22, preferably 12 to 18 carbon atoms, and R 14 and R 15 independently of one another for R 13 or an optionally hydroxy-substituted alkyl radical with 1 to 4 carbon atoms.
  • Amine oxides of the formula (VI) are preferably used in which R 13 and R 14 are C12 / 14 and C12 / 18 coconut alkyl radicals and R 15 is a methyl or a hydroxyethyl radical.
  • Amine oxides of the formula (VI) in which R 13 represents a C12 / 14 or C12 / .8 cocoalkyl radical and R 14 and R 15 have the meaning of a methyl or hydroxyethyl radical are also preferred.
  • alkylamidoamine oxides of the formula (VIII), the alkylamido radical R23CONH being obtained by the reaction of linear or branched carboxylic acids, preferably having 6 to 22, preferably having 12 to 18, carbon atoms, in particular from C12 / 14- or C12 / 18- fatty acids with amines.
  • R 24 represents a linear or branched alkylene group having 2 to 6, preferably 2 to 4 carbon atoms and R 14 and R 15 have the meaning given in formula (VI).
  • the further nonionic surfactants can be present in the agents according to the invention in amounts of 0.1 to 15% by weight, preferably 0.5 to 10% by weight, in particular 1 to 8% by weight, calculated as the active substance, based on the agents.
  • the agents according to the invention can contain anionic surfactants.
  • anionic surfactants are soaps, alkylbenzene sulfonates, secondary alkane sulfonates, olefin sulfonates, alkyl ether sulfonates, glycerin ether sulfonates, methyl ester sulfonates, sulfo fatty acids, alkyl and / or alkenyl sulfates, alkyl ether sulfates, glycerin ether sulfates, (sulfate etherate) sulfate ethersulfate, fatty acid ether sulfate, fatty acid ether sulfate, fatty acid ether sulfate, fatty acid sulfate, sulfate ether, sulfate, ether sulfate, fatty acid ether sulfate, sulfate ether, fatty acid ether sulfate, fatty acid sulf
  • anionic surfactants contain polyglycol ether chains, they can have a conventional, but preferably a narrow, homolog distribution.
  • the anionic surfactants are preferably selected from the group formed by alkyl and / or alkenyl sulfates, alkyl ether sulfates, alkyl benzene sulfonates, monoglyceride (ether) sulfates and alkane sulfonates, in particular fatty alcohol sulfates, fatty alcohol ether sulfates, secondary alkane sulfonates and linear alkyl benzene sulfonates.
  • Alkyl and / or alkenyl sulfates which are also often referred to as fatty alcohol sulfates, are to be understood as meaning the sulfation products of primary alcohols which follow the formula (VIII)
  • R 16 represents a linear or branched, aliphatic alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms and X represents an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium.
  • alkyl sulfates which can be used in the context of the invention are the sulfation products of capron alcohol, caprylic alcohol, capric alcohol, 2-ethylhexyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, petroselachcohol, elaidyl alcohol, Behenyl alcohol and erucyl alcohol and their technical mixtures, which are obtained from high pressure hydrogenation of technical methyl ester fractions or aldehydes from Roelen's oxosynthesis.
  • the sulfation products can preferably be used in the form of their alkali metal salts and in particular their sodium salts.
  • Alkyl sulfates based on Ci6 / 18 tallow fatty alcohols or vegetable fatty alcohols of comparable carbon chain distribution in the form of their sodium salts are particularly preferred.
  • ether sulfates are known anionic surfactants which are produced on an industrial scale by SO3 or chlorosulfonic acid (CSA) sulfation of fatty alcohol or oxo alcohol polyglycol ethers and subsequent neutralization.
  • CSA chlorosulfonic acid
  • ether sulfates are suitable which follow the formula (IX)
  • Typical examples are the sulfates of addition products with an average of 1 to 10 and in particular 2 to 5 mol ethylene oxide onto capronalcohol, caprylic alcohol, 2ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, oleyl alcohol, isostyl alcohol, isostyl alcohol Petselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol and their technical mixtures in the form of their sodium and / or magnesium salts.
  • the ether sulfates can have both a conventional and a narrow homolog distribution. It is particularly preferred to use ether sulfates based on adducts of an average of 2 to 3 mol ethylene oxide with technical C12 / 14 or C12 / 18 coconut oil alcohol fractions in the form of their sodium and / or magnesium salts.
  • Alkylbenzenesulfonates preferably follow the formula (X),
  • R 18 stands for a branched, but preferably linear alkyl radical having 10 to 18 carbon atoms, Ph for a phenyl radical and X for an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium.
  • Dodecylbenzenesulfonates, tetradecylbenzenesulfonates, hexadecylbenzenesulfonates and their technical mixtures in the form of the sodium salts are preferably used.
  • Monoglyceride sulfates and monoglyceride ether sulfates are known anionic surfactants which can be obtained by the relevant methods of preparative organic chemistry.
  • the usual starting point for their preparation is triglycerides, which, if appropriate, are transesterified to the monoglycerides after ethoxylation and subsequently sulfated and neutralized. It is also possible to react the partial glycerides with suitable sulfating agents, preferably gaseous sulfur trioxide or chlorosulfonic acid [cf. EP 0561825 B1, EP 0561999 B1 (Henkel)].
  • the neutralized substances can be subjected to ultrafiltration in order to reduce the electrolyte content to a desired level [DE 4204700 A1 (Henkel)].
  • Overviews of the chemistry of the monoglyceride sulfates are, for example, by A. K. Biswas et al. in J.Am.Oil.Chem.Soc. 37, 171 (1960) and F. U. Ahmed J.Am.Oil.Chem.Soc. 67, 8 (1990).
  • the monoglyceride (ether) sulfates to be used in accordance with the invention follow the formula (XI),
  • R 19 CO stands for a linear or branched acyl radical with 6 to 22 carbon atoms, c, d and e in total for 0 or for numbers from 1 to 30, preferably 2 to 10, and X stands for an alkali or alkaline earth metal.
  • Typical examples of monoglyceride (ether) sulfates suitable for the purposes of the invention are the reaction products of lauric acid monoglyceride, coconut fatty acid monoglyceride, palmitic acid monoglyceride, stearic acid monoglyceride, oleic acid monoglyceride and tallow fatty acid monoglyceride as well as their ethylene oxide adducts or their form of sulfuric acid with sulfuric acid trioxide.
  • Monoglyceride sulfates of the formula (XI) are preferably used in which R 19 CO stands for a linear acyl radical having 8 to 18 carbon atoms. alkanesulfonates
  • Alkane sulfonates are taken to mean compounds of the formula (XII).
  • R 20 and R 21 represent alkyl radicals, where R 20 and R 21 together should not have more than 50 carbon atoms.
  • the agents can expediently contain 0.1 to 20% by weight, preferably 0.25 to 15% by weight, in particular 0.4 to 10% by weight, of anionic surfactants, calculated as the active substance, based on the agents.
  • the rest which is missing by 100% by weight, can be auxiliary substances and additives as well as water.
  • the agents according to the invention can, as usual ingredients or auxiliaries and additives, for example solubilizers such as cumene sulfonate, ethanol, isopropyl alcohol, ethylene glycol, propylene glycol, butyl glycol, diethylene glycol, propylene glycol monobutyl ether, polyethylene or polypropylene glycol ether with molecular weights of 600 to 1,500,000, preferably with a molecular weight from 400,000 to 800,000, or in particular butyl diglycol.
  • solubilizers such as cumene sulfonate, ethanol, isopropyl alcohol, ethylene glycol, propylene glycol, butyl glycol, diethylene glycol, propylene glycol monobutyl ether, polyethylene or polypropylene glycol ether with molecular weights of 600 to 1,500,000, preferably with a molecular weight from 400,000 to 800,000, or in particular butyl diglycol.
  • Abrasive materials such as quartz
  • agents can contain cationic surfactants or biocides, for example glucoprotamine.
  • Suitable builders are zeolites, phyllosilicates, phosphates and ethylenediaminetetraacetic acid, nitrilotriacetic acid, citric acid and its salt, and inorganic phosphonic acids.
  • sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Other bleaching agents are, for example, peroxy carbonate, citrate perhydrates and H2O2-providing peracid salts of peracids such as perbenzoates, peroxyphthalates or diperoxydodecanedioic acid. They are usually used in amounts of 0.1 to 40% by weight.
  • the use of sodium perborate monohydrate in amounts of 10 to 20% by weight and in particular 10 to 15% by weight is preferred.
  • Suitable enzymes are those from the class of proteases, lipase, amylases, cellulases or mixtures thereof.
  • Bacterial strains or fungi such as Bacillus sub- tilis, Bacillus lichenformis and Strptomyces griseus enzymatic active ingredients obtained.
  • Proteases of the subtilisin type and in particular proteases obtained from Bacillus lentes are preferably used. Their proportion can be about 0.1 to 6, preferably 0.2 to 2% by weight.
  • the enzymes can be adsorbed on carriers or embedded in coating substances in order to protect them against premature decomposition.
  • the agents can contain further enzyme stabilizers.
  • enzyme stabilizers For example, 0.5 to 1% by weight sodium formate can be used. It is also possible to use proteases which are stabilized with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme.
  • boron compounds for example boric acid, boron oxide, borax and other alkali metal borates such as the salts of orthoboric acid (H3BO3), metaboric acid (HBO2) and pyrobic acid (tetraboric acid H2B4O7), is particularly advantageous.
  • foam inhibitors When used in the machine washing process, it can be advantageous to add conventional foam inhibitors to the agents.
  • Suitable foam inhibitors contain, for example, known organo-olysiloxanes and / or paraffins or waxes.
  • Foam regulators such as soap, fatty acids, in particular coconut fatty acid and palm kernel fatty acid, may also be included.
  • hardened castor oil salts of long-chain fatty acids, which are preferably in amounts of 0 to 5% by weight and in particular in amounts of 0.5 to 2% by weight, for example sodium, potassium, aluminum, Magnesium and titanium stearates or the sodium and / or potassium salts of behenic acid, and other polymeric compounds are used.
  • the latter preferably include polyvinylpyrrolidone, urethanes and the salts of polymeric polycarboxylates, for example homopolymeric or copolymeric polyacrylates, polymethacrylates and in particular copolymers of acrylic acid with maleic acid, preferably those composed of 50 to 10% by weight of maleic acid.
  • the relative molecular weight of the homopolymers is generally between 1000 and 100000, that of the copolymers between 2000 and 200000, preferably between 50,000 to 120,000, based on the free acid.
  • Water-soluble polyacrylates which are crosslinked, for example, with about 1% of a polyallyl ether of sucrose and which have a relative molecular weight above 1,000,000 are particularly suitable. Examples of these are polymers obtainable under the name Carbopol® 940 and 941.
  • the crosslinked polyacrylates are preferably used in amounts of not more than 1% by weight, particularly preferably in amounts of 0.2 to 0.7% by weight.
  • the agents according to the invention contain 5 to 90, preferably 10 to 80 wt.% Builders, 0.1 to 6 wt.% Detergent enzyme, optionally 0.1 to 40, preferably 0.5 to 30 wt.% Bleaches and auxiliaries and additives , % By weight is to be understood in relation to the average.
  • Another object of the present invention is the use of hydroxy mixed ethers of the formula (I) in washing, rinsing and cleaning agents, in particular for rinsing and cleaning hard surfaces, preferably in the household and in the industrial and institutional fields.
  • Particularly suitable is the use in dishwashing detergents, rinse aids, bathroom cleaners, floor cleaners, cleaners based on the clean shower concept (e.g. bathroom cleaners, which are sprayed on walls and fittings before and after showering, so that the water and soap residues run off better, and thereby Wiping is not necessary), cockpit cleaner (car, plane, ship, motorcycle), window cleaner and all-purpose cleaner.
  • Hard surfaces include Ceramic surfaces, metal surfaces, painted surfaces, plastic surfaces and surfaces made of glass, stone, concrete, porcelain and wood.
  • hydroxy mixed ethers of the formula (I) is particularly preferred for improving the wetting behavior in detergents, dishwashing detergents and cleaning agents, preferably on hard surfaces, in particular in machine dishwashing detergents and / or rinse aids. It is further preferred to use hydroxy mixed ethers of the formula (I) to improve the compatibility with plastics in detergents, dishwashing detergents and cleaning agents, in particular in machine dishwashing detergents and / or rinse aids.
  • the hydroxy mixed ethers of the formula (I) according to the invention are very particularly preferred, optionally in combination with the other surfactants already described, for the simplified preparation of solid detergent formulations. Because of their higher melting points, the hydroxy mixed ethers according to the invention can be more easily incorporated into washing, rinsing and cleaning agent formulations, in particular into solid cleaners. Also preferred is the use of hydroxy mixed ethers of the formula (I) as defoamers in detergents, dishwashing detergents and cleaning agents, in particular in machine dishwashing detergents and / or rinse aids.
  • the hydroxy mixed ethers according to the invention are notable for their good foam-suppressing action, good wetting action, high compatibility, in particular with respect to plastic, and for their higher melting points.
  • the hydroxy mixed ethers according to the invention are suitable for the simplified production of solid formulations due to the high melting points. Likewise, these hydroxy mixed ethers, due to their higher melting points, later dissolve in the cleaning liquor and develop with a time delay and in higher concentration. This effect can be used particularly advantageously in rinse aid applications. Surprisingly, the hydroxy mixed ethers of the invention are particularly spectacular due to their colorless, clear appearance, which makes incorporation into a large number of detergents, dishwashing detergents and cleaning agents possible without a complex bleaching process.
  • the wetting properties of surfactant solutions against plastics were determined in a simplified screening based on the conditions / test parameters in a commercial dishwasher, but without the use of such.
  • plastic test specimens measuring 20 x 5 cm are first cleaned with 1% NaOH and then with isopropanol.
  • the test specimens pretreated in this way are then immersed in the solution to be tested and immediately removed again.
  • the evaluation is carried out visually by drawing up a ranking list or on a scale from 1-5. 5 means that spontaneous tearing of the liquid film occurs and the wetting is completely eliminated.
  • Grade 5 is obtained when water is used.
  • the grade 1 means complete wetting of the plastic surface with an even flow of the liquid film.
  • Grade 1 is obtained using Na-LAS (e.g. Maranil A 55 / COGNIS).
  • PP polypropylene
  • PE polyethylene
  • PC polycarbonate
  • Table 1 The test results are shown in Table 1, V1 to V4 comparative tests and I, II and III representing the examples according to the invention. Table 1:
  • Table 3 shows the melting points of the hydroxy mixed ethers.
  • Table 4 describes the foaming behavior of the surfactants.
  • 2 eggs (approx. 100 to 110 g) were diluted in an electric mixer in a ratio of 1: 1 with water with a hardness of 16 d and stirred for 2 min.
  • 100 g of the resulting emulsion were then in a double-walled measuring cylinder with a Capacity from 2000 ml to 500 ml with 16 d water and tempered to 50 C.
  • the solution was sucked from the bottom of the measuring cylinder with a glass tube. The return was carried out via a second tube, the lower end of which ended at the level of the 2000 ml mark on the measuring cylinder.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)

Abstract

L'invention concerne des hydroxy-éthers mixtes hautement éthoxylés en liaison avec des produits de lavage, de rinçage et de nettoyage, et l'utilisation de tels hydroxy-éthers mixtes utilisés comme agents antimoussants dans des produits de lavage, de rinçage et de nettoyage.
PCT/EP2002/001052 2001-02-01 2002-02-01 Hydroxy-ethers mixtes a haut degre d'ethoxylation utilises comme agents antimoussants WO2002061025A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP02719749A EP1356014B1 (fr) 2001-02-01 2002-02-01 Hydroxy-ethers mixtes a haut degre d'ethoxylation utilises comme agents antimoussants
US10/470,898 US6921744B2 (en) 2001-02-01 2002-02-01 Hydroxy mixed ethers having a high degree of ethoxylation, compositions containing the same and anti-foam uses therefor
ES02719749T ES2373872T3 (es) 2001-02-01 2002-02-01 Hidroxiéteres mixtos con alto grado de etoxilación como antiespumantes.

Applications Claiming Priority (8)

Application Number Priority Date Filing Date Title
DE10104386.6 2001-02-01
DE10104368 2001-02-01
DE10111838 2001-03-13
DE10111838.4 2001-03-13
DE10114172.6 2001-03-23
DE2001114172 DE10114172A1 (de) 2001-03-23 2001-03-23 Handgeschirrspülmittel
DE10116020.8 2001-03-30
DE2001116020 DE10116020A1 (de) 2001-03-30 2001-03-30 Hydroxymischether mit hohem Ethoxylierungsgrad als Entschäumer

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WO2002061025A1 true WO2002061025A1 (fr) 2002-08-08

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EP1764408A1 (fr) 2005-09-14 2007-03-21 Cognis IP Management GmbH Mélanges des agents tensio-actifs pour l'utilisation dans des composition de nettoyage

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DE102004045685A1 (de) * 2004-09-17 2006-04-06 Henkel Kgaa Reinigungsmittelkomponente
DE102007042860A1 (de) * 2007-09-10 2009-03-12 Henkel Ag & Co. Kgaa Reinigungsmittel
JP6272882B2 (ja) 2012-10-11 2018-01-31 ビーエーエスエフ エスイー 水性コーティング用界面活性剤
EP4176029A1 (fr) * 2020-07-02 2023-05-10 Basf Se Composés hydroxyéthers mélangés, procédé de préparation de ces composés et leur utilisation

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WO2001079401A1 (fr) * 2000-04-18 2001-10-25 Cognis Deutschland Gmbh & Co. Kg Detergents et nettoyants
EP1167499A1 (fr) * 2000-06-29 2002-01-02 Cognis Deutschland GmbH Compositions détergentes liquides contenant des hydroxyéthers mélangés

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Publication number Priority date Publication date Assignee Title
EP1764408A1 (fr) 2005-09-14 2007-03-21 Cognis IP Management GmbH Mélanges des agents tensio-actifs pour l'utilisation dans des composition de nettoyage

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US6921744B2 (en) 2005-07-26
US20040063602A1 (en) 2004-04-01

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